CN102936290A - Acetylated corn starch and preparation method thereof - Google Patents
Acetylated corn starch and preparation method thereof Download PDFInfo
- Publication number
- CN102936290A CN102936290A CN201210437344XA CN201210437344A CN102936290A CN 102936290 A CN102936290 A CN 102936290A CN 201210437344X A CN201210437344X A CN 201210437344XA CN 201210437344 A CN201210437344 A CN 201210437344A CN 102936290 A CN102936290 A CN 102936290A
- Authority
- CN
- China
- Prior art keywords
- starch
- sizing
- microwave
- gum
- acetylize
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920002261 Corn starch Polymers 0.000 title claims abstract description 12
- 239000008120 corn starch Substances 0.000 title claims abstract description 9
- 229920002472 Starch Polymers 0.000 claims abstract description 195
- 235000019698 starch Nutrition 0.000 claims abstract description 195
- 239000008107 starch Substances 0.000 claims abstract description 194
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000012065 filter cake Substances 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 4
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 19
- 238000006467 substitution reaction Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 229940099112 cornstarch Drugs 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 abstract description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 abstract description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 abstract description 3
- 235000005822 corn Nutrition 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- 238000004513 sizing Methods 0.000 description 98
- 230000000694 effects Effects 0.000 description 36
- 239000004372 Polyvinyl alcohol Substances 0.000 description 35
- 229920002451 polyvinyl alcohol Polymers 0.000 description 35
- 239000002002 slurry Substances 0.000 description 31
- 238000012360 testing method Methods 0.000 description 19
- 238000009955 starching Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 229920000742 Cotton Polymers 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000835 fiber Substances 0.000 description 10
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000009941 weaving Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920000881 Modified starch Polymers 0.000 description 3
- 239000004368 Modified starch Substances 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 241000863032 Trieres Species 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 235000019426 modified starch Nutrition 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 241000212978 Amorpha <angiosperm> Species 0.000 description 2
- 229920000945 Amylopectin Polymers 0.000 description 2
- 229920000856 Amylose Polymers 0.000 description 2
- 206010020112 Hirsutism Diseases 0.000 description 2
- 240000003183 Manihot esculenta Species 0.000 description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000007244 Zea mays Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000000454 anti-cipatory effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses an acetylated corn starch and a preparation method thereof. The starch comprises, by mass, 100 parts of corn native starch, 8-9 parts of acetic acid vinyl ester, 5-5.2 parts of potassium carbonate and 250-350 parts of deionized water. The preparation method includes producing the corn native starch and the deionized water into a starch suspension and placing in a microwave reactor, reacting for 10-12min under a microwave power of 480-500W at 48-52DEG C, and adding acetic acid vinyl ester and potassium carbonate solution with a concentration of 3% dropwise simultaneously; and regulating the pH to 6.5-7 through a 0.1mol/L hydrochloric acid solution, filtering, washing a filter cake with 50/50 (V/V) ethanol/water solution for 2-3 times, then washing with absolute ethyl alcohol for 2-3 times, subjecting the filter cake to 60-DEG C drying, grinding, 65-mesh sample sieve screening, and drying at 60 DEG C until reaching a constant weight to obtain a product.
Description
Technical field
The present invention relates to weaving and use the modified starch size technology, be specially a kind of acetylize W-Gum and preparation method thereof.
Background technology
Starch is as the main slurry of warp sizing, and it is very extensive to originate, and cheap, but the formality trouble of sizing mixing, sizing performance can not be satisfactory.The appearance of PVA has solved the sizing of hydrophobic fibre, and its remarkable film forming properties is considered to the revolution of warp sizing.But the PVA hard degradation to environment, is considered to unclean slurry.Therefore, the contradiction that solves sizing performance and environmental pollution has become the focus that industry and scholars pay close attention to.Because starch resource is abundant, be easy to degraded, people can utilize the structural characteristics of starch polymer, and starch is carried out chemistry or physical modification, improve the Practical Performance of starch.A thinking that replaces PVA is carried out denaturing treatment to starch exactly, to reach separately or to mix use with acrylic size, get rid of PVA purpose (referring to military current chart, based on the starch solid phase grafting slurry in microwave field research ［ D ］. Tianjin University of Technology, 2003.12).
Acetylated starch claims again acetate starch or starch acetates, is a most important kind in the esterification starch.Be characterized in that the retrogradation of sticking with paste is low, high to the stability of acid, alkali, heat, the transparency of paste is high, freezes molten good stability; Intermolecular difficult formation hydrogen bond, ageing resistance is good, is mainly used in thickening material, stablizer, cakingagent and food starch film processed.At present the acetylated starch of state's production such as American-European, Japanese is mainly the product of low degree of substitution, is applied to food, papermaking, weaving and other industry.In textile industry, acetate starch is mainly used in natural fiber yarn and chemical mixed yarn starching, general and synthetic slurry use mass ratio with between 10 ~ 30%, if adopt superior in quality acetate starch, and being equipped with rational size mixing technology and strict operation and management, it uses mass ratio with can reach 50 ~ 60%.Acetate starch can be used as the main body slurry and uses, mix with acrylic size, polyvinyl alcohol pulp, have the usefulness of good subsides volt filoplume, be suitable for very much the requirement of air-jet loom weaving (referring to Zhou Yongyuan, spinning sizing agent is learned ［ M ］. China Textiles Press, 2004.2).Acetylated starch generally acts on starch milk with acid anhydrides or vinyl acetate and manufactures under alkaline condition, the alkali conditioned reaction system pH with 3% is neutralized to pH6.5～pH7.0 with hydrochloric acid after reaction finishes, then centrifugal, washing, dry, make finished product.At present, immersion method or electric mantle heating method are adopted in the preparation of acetylated starch more, and reaction time consumption is long, efficient is low; Simultaneously, long-time heating also can produce to a certain degree starch structure and destroy.In recent years, microwave heating method began to have obtained preferably effect in organic synthesis field broad research and application.
Microwave be frequency in 300MHz ~ 300GHz scope, the hertzian wave of wavelength about from 1mm to 1m.Its high frequency is to the polarizable medium effect, and the rotation of charged particle or translational speed are very fast, can promote monomer or reaction solution to be rapidly heated, and homogeneous heating, has avoided slow, the shortcoming such as inhomogeneous of being heated of traditional heating mode rate of heating.Because the rotational oscillation dynamic frequency of microwave frequency and chemical group approaches, therefore molecular conformation is changed, activate some group, and to the macromolecular chain not damaged, greatly fast reaction speed (referring to Jin Qinhan etc., microwave chemical ［ M ］. Science Press, 1999.10).The application of microwave current radiotechnology on starch conversion becomes in the recent period study hotspot both at home and abroad.The microwave reaction effect is very complicated, to the effect of organic chemical reactions, not only has heat effect can also change the kinetic property of reaction, reduces the activation energy that reacts, and starch under microwave exposure heat effect and magnetoresistive effect occurs.Heat without thermograde starch inside, in microwave field, starch molecule is done orderly high-frequency vibration, mutually collision, friction, produce heat energy starch is heated up, and other chemical substances react, generate modified starch (referring to Wang Qingcheng etc., Microwave Solid heating method starch-phosphate new synthetic process research ［ J ］. chemistry circular, 2003).With traditional heating carry out chemical reaction compare microwave radiation compare have rate of heating fast, shorten reaction and carry out the time, improve reaction efficiency, optimize the various features such as operation system.But household microwave oven is used in research before this more, lack the devices such as the synthetic necessary stirring of conventional chemical, deoxygenation, backflow, dropping, minute water, therefore it is unsatisfactory to prepare effect, again because uncontrollable temperature, so reaction process is difficult to control, and is repeatable poor, and cause the reactant volatilization serious, when serious in addition have presence of fire danger (referring to Li Dongmei etc., the preparation and property of the acrylic acid-grafted slurry of potato starch ［ J ］ in the microwave field. cotton textile technology, 2004.1).
Summary of the invention
For the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is: a kind of acetylize W-Gum and preparation method thereof is provided.It is low, mobile high that this starch has viscosity, and swelling behavior is good, paste liquid transparency is high, and stability is high, and resistance to deterioration is strong; High to the polyester cotton blended yarn adhesive power, good film-forming property, the advantage such as serous coat is tough, sizing performance is superior.This starch is owing to be to prepare in microwave field, has the energy-and time-economizing, reaction efficiency is high, reaction conditions relaxes, be convenient to product separation, process is easy to control, repeatability is high, and pollution-free in the production process, the characteristics such as security height.
The technical scheme that the present invention solves described starch technical problem is, designs a kind of acetylize W-Gum, and the raw materials quality that it is characterized in that this starch forms umber and is: 100 parts of native cornstarchs; 8 ~ 9 parts of vinyl-acetic esters; 290 ~ 310 parts of 5 ~ 5.2 parts in salt of wormwood and deionized waters; The substitution value of this starch is 0.09 ~ 0.1.
The technical scheme that the present invention solves described preparation method's technical problem is, designs a kind of preparation method of acetylize W-Gum, and this preparation method adopts the raw materials quality of acetylize W-Gum of the present invention to form and following processing step:
(1) microwave assisting method prepares the acetylize W-Gum:
The native cornstarch of described umber and deionized water are made starch suspension, be transferred in two mouthfuls of flasks of 250mL, flask is placed in the microwave reactor, connect condensation reflux unit, open magnetic agitation, microwave output power 480 ~ 500W is set, at 48 ~ 52 ℃ of lower reaction 10 ~ 12min of temperature, slowly drips simultaneously the solution of potassium carbonate of esterifying agent vinyl-acetic ester and catalyst concn 3% by constant pressure funnel;
(2) separation of product: after reaction finishes; close microwave; product is taken out; hydrochloric acid soln with 0.1mol/L is regulated pH value to 6.5 ~ 7, filters, and filter cake is with deionized water washing 2-3 time; use again absolute ethanol washing 2-3 time; filter cake is dried under 60 ℃, pulverizes, crossed 65 order sub-sieves, under 60 ℃, dry to constant weight again, namely obtain pulverous acetylize W-Gum.
Compared with prior art, innovative point of the present invention mainly contains following two aspects:
1. the present invention adopts microwave assisting method to prepare acetylated starch, compares with the traditional water bath method, and speed of reaction has improved decades of times, has the production efficiency height, the time spent is short, energy consumption is low, the advantage that production process is environment friendly and pollution-free.In addition; though microwave assisting method prepares acetylated starch in the past research was arranged; but most of household microwave oven that adopts; or under constant power, carry out; energy enhance esterification speed has the uncontrollable problem of temperature of reaction system, though also can cause because internal temperature is too high starch pasting even coking; reaction process is uncontrollable, poor reproducibility.The present invention uses the MCR-3 microwave chemical reactor to prepare acetylated starch first, and temperature of reaction can realize intelligent control by automatic regulation output power, and temperature of reaction has been discussed in the microwave field on this basis on the impact of acetylize effect.The preparation process controllability strengthens greatly, and circulation ratio is high, and this technology can be used for the production of extensive acetylated starch, and the suitability for industrialized production for preparing acetylated starch for microwave provides new thinking.
2. in application facet; this product is owing to be synthetic in microwave field; therefore under the acting in conjunction of microwave exposure sex change (physical modification) and acetylize modification (chemical modification); physicochemical property has obtained significant lifting, and not only the viscosity of product is low, good stability; and water-soluble; swelling property, resistance to deterioration have had obvious improvement, and the improvement of these a series of physicochemical properties finally becomes the immanent cause that starch slurry improves with performance.The sizing experimental result shows, when substitution value is in 0.09 ~ 0.1, and acetylated starch of the present invention; sizing performance comprises extension at break, and breaking tenacity is significantly improved than ative starch, and filoplume docile rate; the indexs such as wear resisting property are then close to PVA, and particularly remarkable with the enhancing of wear resistance.Because the wear resistance of sizing is subjected to the perviousness of slurries, coating and film-forming properties, filoplume pastes volt property, and the impact of all many-sided factors such as by force stretching property of sizing, so its combined reaction has gone out slurries to the adhesive capacity of yarn and the inherent situation of sizing.So the abrasion resistance of sizing directly affects the weavability of sizing, be considered to most important sizing quality index.
Show based on the above results, acetylated starch of the present invention is applied to wash/starching of cotton type yarn in, its sizing quality obviously improves, be a kind of excellent performance, cheap, be convenient to produce and the environmental protection slurry of environmental sound.Aspect substitution for PVA, have great potentiality.
Description of drawings
Fig. 1 is the infrared spectra comparison diagram of a kind of embodiment of acetylated starch of the present invention and ative starch; Wherein, curve A is the ative starch infrared spectrum; Curve B is acetylated starch infrared spectrum of the present invention;
Fig. 2 is the awkward silence at a meeting emission scan sem image of a kind of embodiment of acetylated starch of the present invention and ative starch, wherein,
Fig. 2 (1) is the FESEM image after the particle of ative starch amplifies 2000 times;
Fig. 2 (2) is the FESEM image after the particle of ative starch amplifies 9000 times;
Fig. 2 (3) is the FESEM image after the particle of acetylated starch of the present invention amplifies 2000 times;
Fig. 2 (4) is the FESEM image after the particle of acetylated starch of the present invention amplifies 9000 times;
Fig. 3 is the X-ray diffraction spectrogram of a kind of embodiment of acetylated starch of the present invention and ative starch; Wherein, curve A is ative starch X-ray diffraction spectrogram; Curve B is acetylated starch X-ray diffraction spectrogram of the present invention;
Fig. 4 is the sizing of a kind of embodiment of acetylated starch of the present invention and the outward appearance comparison diagram of raw yarn, ative starch sizing and PVA sizing, wherein,
Fig. 4 (1) is for washing/cotton (T/C 65/35) raw yarn figure;
Fig. 4 (2) is ative starch sizing figure;
Fig. 4 (3) is PVA sizing figure;
Fig. 4 (4) is acetylated starch sizing figure of the present invention;
Fig. 5 is the sizing appearance effect figure of ative starch sizing behind the different number of times of A-DATA2071.TM obvolvent trier friction, wherein,
Fig. 5 (1) is the sizing appearance effect figure behind the ative starch sizing wear resistant 0 time;
Fig. 5 (2) is the sizing appearance effect figure behind the ative starch sizing wear resistant 50 times;
Fig. 5 (3) is the sizing appearance effect figure behind the ative starch sizing wear resistant 100 times;
Fig. 5 (4) is the sizing appearance effect figure behind the ative starch sizing wear resistant 150 times;
Fig. 5 (5) is the sizing appearance effect figure behind the ative starch sizing wear resistant 200 times;
Fig. 5 (6) is the sizing appearance effect figure behind the ative starch sizing wear resistant 250 times;
Fig. 6 is the sizing appearance effect figure of PVA sizing behind the different number of times of A-DATA2071.TM obvolvent trier friction, wherein,
Fig. 6 (1) is the sizing appearance effect figure behind the PVA sizing wear resistant 0 time;
Fig. 6 (2) is the sizing appearance effect figure behind the PVA sizing wear resistant 50 times;
Fig. 6 (3) is the sizing appearance effect figure behind the PVA sizing wear resistant 100 times;
Fig. 6 (4) is the sizing appearance effect figure behind the PVA sizing wear resistant 150 times;
Fig. 6 (5) is the sizing appearance effect figure behind the PVA sizing wear resistant 200 times;
Fig. 6 (6) is the sizing appearance effect figure behind the PVA sizing wear resistant 250 times;
Fig. 7 is the sizing appearance effect figure of sizing behind the different number of times of A-DATA2071.TM obvolvent trier friction of a kind of embodiment of acetylated starch of the present invention, wherein,
Fig. 7 (1) is the sizing appearance effect figure behind the acetylated starch sizing wear resistant of the present invention 0 time;
Fig. 7 (2) is the sizing appearance effect figure behind the acetylated starch sizing wear resistant of the present invention 50 times;
Fig. 7 (3) is the sizing appearance effect figure behind the acetylated starch sizing wear resistant of the present invention 100 times;
Fig. 7 (4) is the sizing appearance effect figure behind the acetylated starch sizing wear resistant of the present invention 150 times;
Fig. 7 (5) is the sizing appearance effect figure behind the acetylated starch sizing wear resistant of the present invention 200 times;
Fig. 7 (6) is the sizing appearance effect figure behind the acetylated starch sizing wear resistant of the present invention 250 times.
Embodiment:
Further narrate the present invention below in conjunction with embodiment and accompanying drawing.
A kind of acetylize W-Gum of the present invention's design (being called for short acetylated starch or starch, referring to Fig. 1-7) is characterized in that the raw materials quality composition umber of this starch is: 100 parts of native cornstarchs; 8 ~ 9 parts of vinyl-acetic esters; 290 ~ 310 parts of 5 ~ 5.2 parts in salt of wormwood and deionized waters.
Structural characterization and the analysis of physical and chemical property of acetylated starch of the present invention following (referring to Fig. 1-3).
The stretching vibration of ative starch association hydroxyl O-H key 3400 ~ 3200cm in infrared spectrogram (referring to Fig. 1)
-1The place shows as a wide and strong absorption peak, 2930cm
-1The place is starch carbochain skeleton C-H key symmetric vibration absorption peak, 1152 ~ 1015cm
-1For starch ehter bond C-O-C antisymmetric stretching vibration absorption peak (referring to P.Lanthong, R.Nuisin, S.Kiatkamjornwong, Graftcopolymerization, characterization, and degradation of cassava starch-g-acrylamide/itaconic acid superabsorbents. ［ J ］ .Carbohydrate Polymer.SCI, 2006.10; P.Lanthong, R.Nuisin, S.Kiatkamjornwong, the preparation of tapioca (flour) graft acrylamide/methylene-succinic acid super absorbent resin characterizes and the degradation property analysis. ［ J ］. carbohydrate .SCI, 2006.10).Contrast by acetylated starch and ative starch infrared spectra finds that acetylated starch is at 1731cm
-1The stretching vibration absorption peak of C=O of bonding appears in the place, at 1380cm
-1Methyl-CH appears in the place
3The flexural vibration absorption peak, at 1248cm
-1The place stretching vibration absorption peak of C-O singly-bound occurred (referring to Navdeep Singh Sodhi, Narpinder Singh, Characteristics of acetylated starchesprepared using starches separated from different rice cultivars ［ J ］ .Journal of FoodEngineering.SCI, 2005.9; Navdeep Singh Sodhi, Narpinder Singh, the acetylated starch characteristic research ［ J ］ of separating starch preparation from different kind rice. food engineering .SCI, 2005.9).The appearance of above characteristic peak shows has introduced acetyl group on the native cornstarch macromole.
Fig. 2 is respectively ative starch, and the acetylated starch particle amplifies the awkward silence at a meeting emission scan Electronic Speculum figure of 2000 times and 9000 times.Can be found out that by Fig. 2 scanning electron microscope (SEM) photograph that the shape of native cornstarch particle mostly is is circular, angular, Polygons etc., surface smoothing, regular.Compare with ative starch; large change does not occur in the acetylated starch granule-morphology; this is because the substitution reaction of starch mainly occurs in the surface of gel phase interior (amorphous phase) or crystallite; and the starch crystalline state closely is difficult to be infiltrated by chemical reagent owing to piling up mutually, so acetylize can not cause the noticeable change of a pattern.Part acetate starch regular particles degree descends, occur unevenly, hole appears in a few granules surface, and the vestige that may be stayed by caustic corrosion is (referring to Wei Yanjie, adopt environmentally friendly technology to prepare two kinds of acetic acid vinegar starch and performance comparative studies ［ D ］ thereof. Southwestern University, 2010.5).
Fig. 3 is former W-Gum, the X-ray diffraction spectrogram of acetylated starch.As seen from Figure 3, W-Gum is 15.0 °, 17.1 °, 17.8 ° and 23.0 ° at 2 θ and locates stronger diffraction peak, shows that W-Gum belongs to typical A type crystalline texture.Result of study before shows that microwave can make Type B starch change the A type into, but the crystallization type of A type starch is changed, and through after the microwave treatment, A type starch crystals degree improves.This is owing to starch interior molecules in the microwave processing process is in very active state; its medium chain starch molecule and a starch molecule move; chain starch molecule and chain starch molecule on every side; (starch is amylopectin to prop up the starch molecule end; propping up starch molecule is tree structure; bear side chain (B chain) by main chain (C chain); bear side chain (A chain) by side chain again; the A chain is the end of chain; similar to amylose starch on the structure; easily and amylose starch or other amylopectin end under Hyarogen-bonding, associate; be arranged in parallel with each other; stacking formation is orderly crystalline network closely); prop up starch molecule and form double-spiral structure with the terminal mutually winding of a starch molecule; cause molecular arrangement more orderly; crystallinity is stronger (referring to peaceful core; Cheng Xuexun; Zhao Siming etc., microwave is on the impact ［ J ］ of Starch rice physicochemical characteristic. Hua Zhong Agriculture University's journal. and, 2009.3).
In the diffractogram (Fig. 3) of acetylated starch, be respectively 15.0 °, 17.2 °, 17.9 ° and 22.9 ° of diffraction peaks of locating at 2 θ and still exist, illustrate that the crystal formation of acetylated starch does not change, still be the A type.This and result of study before match.By MDI-Jade software, in conjunction with anticipatory remark mountain method, can be calculated native cornstarch degree of crystallinity is 27.9 °, and the degree of crystallinity of acetylated starch of the present invention does not only improve, slightly reduce on the contrary, and be 25.1 °.Because the introducing of ethanoyl brings space steric effect, has increased the steric restriction of starch polymer, has hindered the orientation movement of starch polymer chain in the microwave field, intermolecular being difficult for is arranged in parallel, and hindered the generation of new microcrystalline structure, so degree of crystallinity does not improve.Again because in the acetylization reaction process, along with the starch granule is destroyed, and the ethanoyl of introducing so that on the starch polymer effect between the hydroxyl weaken, cause between starch molecule and the intramolecular hydrogen bond reaction force attenuation, thus the crystalline network of the starch that weakened.Simultaneously, the existence of ethanoyl makes the extension of distance between the starch chain of pars amorpha, and then cause the interior interchain of crystallizing field apart from increase, a small amount of reaction reagent infiltrates through the crystalline region and reacts, the double-spiral structure of long-range order suffers destruction to a certain degree in the starch granule, the result causes degree of crystallinity to descend (referring to Cherif Ibrahima Khalil Diop, Hai Long Li, Bi Jun Xie, John Shi, Impact of the catalytic activity of iodine on the granule morphology, crystallinestructure, thermal properties and water solubility of acetylated corn (Zea mays) starch synthesized under microwave assistance ［ J ］ .Industrial Crops andProducts.SCI, 2011.3; Cherif Ibrahima Khalil Diop, Hai Long Li, Bi Jun Xie; JohnShi, the catalysis of iodine activity prepares acetylize W-Gum granule form, crystalline structure to microwave assisting method; thermomechanical property and water miscible impact ［ J ］. manufacturing crops and goods .SCI, 2011.3).Because esterification mainly occurs in pars amorpha and crystallite surface, thus can not cause large destruction to the crystalline region, though so acetylated starch degree of crystallinity decline is arranged, not obvious.
Fig. 1; the analytical results of Fig. 2 and Fig. 3 shows that preparation method of the present invention has finished the acetylization reaction of ative starch in microwave field, has introduced acetyl group at starch polymer; the degree of crystallinity of starch descends to some extent, and crumb structure has been subject to destruction to a certain degree.Because the introducing of acetyl group; changed to a great extent the physicochemical property of acetylated starch; as solvability, swelling property have been improved; rheological property, viscosity characteristics, paste liquid stability, anti-aging rise ability have been improved; and adhesion property etc., and the immanent cause that the raising of these performances also is the sizing performance of acetylated starch to be greatly improved compared to native cornstarch.
The present invention has designed the preparation method (abbreviation preparation method) of acetylize W-Gum simultaneously, and this preparation method adopts the raw materials quality umber of acetylize W-Gum of the present invention to form and following processing step:
(1) microwave assisting method prepares the acetylize W-Gum: native cornstarch (abbreviation ative starch) and deionized water according to described umber are made starch suspension, be transferred in two mouthfuls of flasks of 250mL, again flask is placed in the microwave reactor, connects condensation reflux unit, open magnetic agitation; Set microwave output power, temperature of reaction is behind the variablees such as time, open microwave, embodiment reacts 10 ~ 12min under the microwave power of 480 ~ 500W, 48 ~ 52 ℃ of temperature of reaction slowly drip the solution of potassium carbonate of esterifying agent vinyl-acetic ester and catalyst concn 3% simultaneously by constant pressure funnel.
(2) separation of product: after reaction finishes; close microwave, product is taken out, the pH value to 6.5 of the hydrochloric acid soln conditioned reaction liquid of usefulness 0.1mol/L ~ 7; filter; filter cake is used absolute ethanol washing 2-3 time again with deionized water washing 2-3 time, with filter cake oven dry under 60 ℃; pulverize; cross 65 order sub-sieves, under 60 ℃, dry to constant weight again, obtain pulverous acetylize W-Gum of the present invention.
The present invention measures the substitution value of acetylize W-Gum.The measuring method of acetylize W-Gum substitution value mainly with reference to People's Republic of China (PRC) weaving modified starch size industry standard commonly used (referring to FZ/T 15001-2008[S]. the National Development and Reform Commission of the People's Republic of China (PRC), 2008.9).The substitution value of starch of the present invention is 0.09 ~ 0.1.
Acetylize W-Gum preparation method experimental instrument and equipment of the present invention comprises: the MCR-3 microwave chemical reactor; DF-101S type heat collecting type constant-temperature heating magnetic stirring apparatus; the multiplex vacuum pump of SHB-Ш circulating water type; the air blast electrically heated drying cabinet; ZD-85 digital display gas bath constant temperature oscillator, the FA2004N electronic analytical balance.The used plant and instrument of preparation method of the present invention is routine instrument device, and cost is low, and is easy to operate, and technology maturation is applicable to industrial application.
For acetylated starch being described for washing/adhesive power of silk/cotton blended yarn, the present invention is to testing with the adhesive power of washing after the acetylated starch starching/cotton (T/C 65/35) blended roving, and its starching and testing method are:
Lightly on aluminum alloy frame, (noting can not making it that elongation is arranged when the rove bar) is stand-by with the rove bar.In the 2000ml beaker, add a certain amount of distilled water, make the slurries of 1% concentration with starch size, put into 95 ℃ of thermostat water bath temperature adjustment 30min after adding a cover.Make slurry temperature be raised to 95 ℃, be incubated one hour, stand-by.Ready sample and framework are immersed in the slurries, press simultaneously manual time-keeping, be about to framework during dipping 5min and propose, hang up nature and dry.The sample that has dried is cut under framework, and at constant temperature, (65%, 20 ℃ of relative humidity) places 24h in the humidity room, then tests the ultimate strength of rove in the test of ultimate strength instrument.
In order to contrast the adhesion property of acetylize W-Gum and former W-Gum, PVA slurries, the present invention is respectively to ative starch, and the adhesive power of washing after the PVA starching/cotton (T/C 65/35) blended roving is tested.Acetylated starch substitutes with ative starch, PVA respectively in prescription, the same acetylated starch of all the other conditions.
The present invention uses the full-automatic sample single end sizing of ASS3000 type machine that acetylated starch is washed/the starching experiment of cotton (T/C 65/35) blending spun yarn, and the performances such as the intensity of sizing, elongation, wear-resisting, filoplume are tested.Its method for sizing is: be 6% slurry with distilled water configuration solid content, be heated to 95 ℃ of insulations 1 hour, obtain the starching slurries, carry out the starching experiment at the full-automatic sample single end sizing of ASS3000 type machine, the slasher sizing machine significant parameter is: 90 ℃ of sizing temperatures, speed of a motor vehicle 35m/min, 80 ℃ of oven temperatures, squeezing roller pressure 0.2mpa.Obtain the sizing that to test and test its performance.
In order to contrast the performance of acetylated starch and PVA, former W-Gum sizing, the present invention is simultaneously to testing with the sizing after PVA, the former W-Gum starching.Acetylated starch substitutes with PVA and ative starch respectively in prescription, remaining same acetylated starch.
The below provides specific embodiments of the invention.Specific embodiment only is in order to further describe the present invention, not limit claim of the present invention.
Embodiment 1
Take by weighing the 30g W-Gum, the starch suspension with the deionized water configuration quality mark 25% of certain volume is transferred in two mouthfuls of flasks of 250mL, and flask is placed in the MCR-3 microwave chemical reactor, connects condensation reflux unit, opens magnetic agitation.Set microwave output power, temperature of reaction behind the variablees such as time, is opened microwave, at 50 ℃ of lower reaction 12min, slowly drips simultaneously the K of esterifying agent vinyl-acetic ester VAc 2.9mL and catalyst concn 3% by constant pressure funnel
2CO
3Solution 51.2mL.
After reaction finishes; close microwave, product is taken out, regulate pH value to 6.5 ~ 7 with the hydrochloric acid soln of 0.1mol/L; filter; filter cake is used absolute ethanol washing twice again with the deionized water washed twice, with filter cake oven dry under 60 ℃; pulverize; cross 65 order sub-sieves, under 60 ℃, dry to constant weight again, namely obtain pulverous acetylize W-Gum of the present invention.
Acetylize validity check: the measuring method of acetylated starch substitution value mensuration correlation parameter in the joint in the reference.Present embodiment substitution value and reaction efficiency data are as calculated listed in table 1, and structural characterization is referring to Fig. 1, Fig. 2 and Fig. 3.
Embodiment 2
Take by weighing the 30g W-Gum, the starch suspension with the deionized water configuration quality mark 25% of certain volume is transferred in two mouthfuls of flasks of 250mL, and flask is placed in the MCR-3 microwave chemical reactor, connects condensation reflux unit, opens magnetic agitation.Set microwave output power, temperature of reaction behind the variablees such as time, is opened microwave, at 60 ℃ of lower reaction 12min, slowly drips simultaneously the K of esterifying agent vinyl-acetic ester VAc 2.9mL and catalyst concn 3% by constant pressure funnel
2CO
3Solution 51.2mL, remaining with embodiment 1.
Present embodiment substitution value and reaction efficiency as calculated listed in table 1.
Embodiment 3
Take by weighing the 30g W-Gum, the starch suspension with the deionized water configuration quality mark 25% of certain volume is transferred in two mouthfuls of flasks of 250mL, and flask is placed in the MCR-3 microwave chemical reactor, connects condensation reflux unit, opens magnetic agitation.Set microwave output power, temperature of reaction behind the variablees such as time, is opened microwave, at 50 ℃ of lower reaction 20min, slowly drips simultaneously the K of esterifying agent vinyl-acetic ester VAc 2.9mL and catalyst concn 3% by constant pressure funnel
2CO
3Solution 51.2mL, remaining with embodiment 1.
Present embodiment substitution value and reaction efficiency as calculated listed in table 1.
Embodiment 4
Take by weighing the 30g W-Gum, the starch suspension with the deionized water configuration quality mark 25% of certain volume is transferred in two mouthfuls of flasks of 250mL, and flask is placed in the MCR-3 microwave chemical reactor, connects condensation reflux unit, opens magnetic agitation.Set microwave output power, temperature of reaction behind the variablees such as time, is opened microwave, at 50 ℃ of lower reaction 12min, slowly drips simultaneously the K of esterifying agent vinyl-acetic ester VAc 4.3mL and catalyst concn 3% by constant pressure funnel
2CO
3Solution 51.2mL, remaining with embodiment 1.
Present embodiment substitution value and reaction efficiency as calculated listed in table 1.
Embodiment 5
Take by weighing the 30g W-Gum, the starch suspension with the deionized water configuration quality mark 25% of certain volume is transferred in two mouthfuls of flasks of 250mL, and flask is placed in the MCR-3 microwave chemical reactor, connects condensation reflux unit, opens magnetic agitation.Set microwave output power, temperature of reaction behind the variablees such as time, is opened microwave, at 50 ℃ of lower reaction 12min, slowly drips simultaneously the K of esterifying agent vinyl-acetic ester VAc 2.9mL and catalyst concn 3% by constant pressure funnel
2CO
3Solution 64mL, remaining with embodiment 1.
Present embodiment substitution value and reaction efficiency as calculated listed in table 1.
Table 1 embodiment 1 compares with substitution value and the reaction efficiency of embodiment 2 ~ 5
Embodiment 6
In the 2000mL beaker, add 1980mL distilled water; the 20g substitution value is the slurries that 0.09 ~ 0.01 acetylated starch slurry is made 1% concentration; put into 95 ℃ of thermostat water bath temperature adjustment 30min after adding a cover, continue in heating and the insulating process to stir mixing speed 125 ~ 150r/min.Make slurry temperature be raised to 95 ℃, be incubated one hour, stand-by.
Ready sample and framework are immersed in the slurries, press simultaneously manual time-keeping, be about to framework during dipping 5min and propose, hang up nature and dry.
The sample that has dried is cut under framework, and at constant temperature, (65%, 20 ℃ of relative humidity) places 24h in the humidity room, then tests the ultimate strength of rove in the test of ultimate strength instrument.Test result is 76.8N.
Comparative Examples 1
For acetylated starch being described to washing/adhesiving effect of silk/cotton blended yarn, the present invention has done the experiment of rove adhesive power to the ative starch slurries simultaneously.Acetylated starch substitutes with ative starch in prescription, remaining with embodiment 6.Test result is 62.9N.
Comparative Examples 2
For acetylated starch being described to washing/adhesiving effect of silk/cotton blended yarn, the present invention has done the experiment of rove adhesive power to the PVA slurries simultaneously.Acetylated starch substitutes with PVA in prescription, remaining with embodiment 6.Test result is 73.5N.
Embodiment 6 and Comparative Examples 1, Comparative Examples 2 comparative illustration, acetylated starch of the present invention to wash/adhesive power of silk/cotton blended yarn also a little more than the PVA slurry, can overcome the PVA slurry to the shortcoming of hydrophobic fibre adhesivity deficiency far above unmodified former W-Gum.
Embodiment 7
Be 6% acetylated starch slurry with distilled water configuration solid content, be heated to 95 ℃ of insulations 1 hour, obtain the starching slurries.Carry out the starching experiment at the full-automatic sample single end sizing of ASS3000 type machine, the slasher sizing machine significant parameter is: 90 ℃ of sizing temperatures, and speed of a motor vehicle 35m/min, 80 ℃ of oven temperatures, squeezing roller pressure 0.2mpa namely obtains the sizing that can test and tests its performance.
Test result is referring to table 2, and the sizing outward appearance is referring to Fig. 4 (4), and the sizing wear resistant outward appearance is referring to Fig. 7 (1)-7(6).
Comparative Examples 3
In order to contrast the performance of acetylated starch of the present invention and ative starch sizing, the present invention is simultaneously to testing with the sizing after the ative starch starching.Acetylated starch substitutes with ative starch in prescription, remaining with embodiment 7.Test result is referring to table 2, and the sizing outward appearance is referring to Fig. 4 (2), and the sizing wear resistant outward appearance is referring to Fig. 5 (1)-5(6).
Comparative Examples 4
In order to contrast the performance of acetylated starch of the present invention and PVA sizing, the present invention is simultaneously to testing with the sizing after the PVA starching.Acetylated starch substitutes with PVA in prescription, remaining with embodiment 7.Test result is referring to table 2, and the sizing outward appearance is referring to Fig. 4 (3), and the sizing wear resistant outward appearance is referring to Fig. 6 (1)-6(6).
Table 2 embodiment 7, Comparative Examples 3, Comparative Examples 4 sizing performance parameters are relatively
Compare with Fig. 4 (1), Fig. 4 (2), Fig. 4 (3) by Fig. 4 (4), the film-forming properties of PVA slurry is best, and the film-forming properties of acetylated starch slurry of the present invention is slightly poorer than PVA, but is better than ative starch.By Fig. 5 (1)-5(6) and Fig. 6 (1)-6(6) and Fig. 7 (1)-7(6) compare; after inferior through identical friction; the hairiness number that the PVA sizing produces is minimum; the ative starch hairiness number is maximum; the destroyed situation of yarn is also the most serious; the extent of damage of acetylated starch sizing of the present invention is slightly larger than PVA, but is significantly less than ative starch.
Table 2 show when substitution value 0.09 ~ 0.01 the time; the more unmodified ative starch sizing performance of acetylated starch sizing performance of the present invention is greatly improved; partial properties index and PVA sizing approach, and the most remarkable with the increase of the enhancing of wear resistance and filoplume reduced rate.This is because microwave exposure and acetylize modification produce the result of dual improvement effect to the physico-chemical property of starch.First, in microwave field, starch polymer generation high-frequency vibration, cause molecular rupture, degraded has to a certain degree occured in starch, short and small chain starch and an easier stripping from granule of starch, improved the flowability of starch, the osmosis of slurry increases, and has strengthened the intensity of the bonding glue-line between the yarn internal fiber, thereby has improved brute force and the mechanical property such as wear-resisting of sizing.The second, be oxy radical owing to introduce ethanoyl, certain wetting ability is arranged, it has improved the water-soluble of starch size, so that the acetate starch macromole chain link of aquation is easier of fiber surface, diffusion infiltrates; The Sauerstoffatom of ethanoyl can be by the hydroxy combining formation hydrogen bond with cotton fibre of share electron pair not; and its with alkyl; can pass through normal form power again; ester group in polyster fibre is combined; principle according to similar compatibility; it has good avidity to this two types of fibers, thereby has improved adhesivity, and film-forming properties improves.Owing to swelling power and the gelatinization property enhancement of acetylated starch, slurry is easier, and certain viscosity also is conducive to the film forming of starch to the fiber surface diffusion again, and yarn coating enhancing is so filoplume docile rate improves.The 3rd; because the introducing of ethanoyl has reduced the hydrogen bond association between starch polymer; Intermolecular Forces weakens; the retardation of main chain inward turning reduces, and the autokinetic movement ability is strong, so the starch polymer rotation is more flexible; kindliness improves; played the effect of plasticising, therefore strengthened the toughness of serous coat, made by force stretching property increase.Because the serous coat snappiness improves, it is not easily broken to rub through external force, thereby wear resistance strengthens simultaneously.The sizing performance test result shows; the sizing performance index of acetylated starch of the present invention has great improvement than ative starch; at film-forming properties with to the affinity of polyester fiber significant raising has been arranged; wherein filoplume and wear-resistant index are near PVA; proving whole or in part substitution for PVA of acetylated starch of the present invention, is a kind of new green environment protection slurry that has potentiality.
Claims (2)
1. an acetylize W-Gum is characterized in that the raw materials quality composition umber of this starch is: 100 parts of native cornstarchs; 8 ~ 9 parts of vinyl-acetic esters; 290 ~ 310 parts of 5 ~ 5.2 parts in salt of wormwood and deionized waters; The substitution value of this starch is 0.09 ~ 0.1.
2. the preparation method of an acetylize W-Gum, this preparation method adopt the raw materials quality of the described acetylize W-Gum of claim 1 to form and following processing step:
(1) microwave assisting method prepares the acetylize W-Gum: the native cornstarch of described umber and deionized water are made starch suspension, be transferred in two mouthfuls of flasks of 250mL, flask is placed in the microwave reactor, connect condensation reflux unit, open magnetic agitation, microwave output power 480 ~ 500W is set, at 48 ~ 52 ℃ of lower reaction 10 ~ 12min of temperature, slowly drips simultaneously the solution of potassium carbonate of esterifying agent vinyl-acetic ester and catalyst concn 3% by constant pressure funnel;
(2) separation of product: after reaction finishes; close microwave; product is taken out; hydrochloric acid soln with 0.1mol/L is regulated pH value to 6.5 ~ 7, filters, and filter cake is with deionized water washing 2-3 time; use again absolute ethanol washing 2-3 time; filter cake is dried under 60 ℃, pulverizes, crossed 65 order sub-sieves, under 60 ℃, dry to constant weight again, namely obtain pulverous acetylize W-Gum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210437344.XA CN102936290B (en) | 2012-11-06 | 2012-11-06 | Acetylated corn starch and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210437344.XA CN102936290B (en) | 2012-11-06 | 2012-11-06 | Acetylated corn starch and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102936290A true CN102936290A (en) | 2013-02-20 |
| CN102936290B CN102936290B (en) | 2015-05-27 |
Family
ID=47695220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210437344.XA Expired - Fee Related CN102936290B (en) | 2012-11-06 | 2012-11-06 | Acetylated corn starch and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102936290B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418777A (en) * | 2015-12-19 | 2016-03-23 | 陈虹 | Synthetic process of acetylated starch |
| CN105542021A (en) * | 2016-02-01 | 2016-05-04 | 广西民族大学 | Method for producing starch acetate |
| CN112674209A (en) * | 2020-12-28 | 2021-04-20 | 华中农业大学 | Method for preparing acetylated starch capable of improving yield of fermented butyric acid |
| CN114805619A (en) * | 2022-06-15 | 2022-07-29 | 河南工业大学 | Preparation method of acetylated modified high-amylose corn starch |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1534423A (en) * | 2003-11-14 | 2004-10-06 | 四川大学 | Temperature measuring and controlling device of microwave chamical reactor |
| CN101579617A (en) * | 2009-01-20 | 2009-11-18 | 江苏工业学院 | Microwave chemical reactor |
| CN101863994A (en) * | 2010-06-18 | 2010-10-20 | 罗代洪 | Method for preparing esterified starch by microwave |
| JP4942856B1 (en) * | 2011-11-25 | 2012-05-30 | 日本食品化工株式会社 | Meat product improvers and livestock products |
| CN102698682A (en) * | 2012-05-31 | 2012-10-03 | 苏州市金翔钛设备有限公司 | Constant temperature control system for microwave chemical reactor |
-
2012
- 2012-11-06 CN CN201210437344.XA patent/CN102936290B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1534423A (en) * | 2003-11-14 | 2004-10-06 | 四川大学 | Temperature measuring and controlling device of microwave chamical reactor |
| CN101579617A (en) * | 2009-01-20 | 2009-11-18 | 江苏工业学院 | Microwave chemical reactor |
| CN101863994A (en) * | 2010-06-18 | 2010-10-20 | 罗代洪 | Method for preparing esterified starch by microwave |
| JP4942856B1 (en) * | 2011-11-25 | 2012-05-30 | 日本食品化工株式会社 | Meat product improvers and livestock products |
| CN102698682A (en) * | 2012-05-31 | 2012-10-03 | 苏州市金翔钛设备有限公司 | Constant temperature control system for microwave chemical reactor |
Non-Patent Citations (5)
| Title |
|---|
| 孙平等: ""玉米淀粉的酯化反应受微波催化的影响"", 《粮油加工与食品机械》 * |
| 张燕萍: "《变性淀粉》", 31 January 2001 * |
| 房键等: ""微波法制备淀粉醋酸酯的研究"", 《盐城工学院学报(自然科学版)》 * |
| 杨建洲等: ""醋酸酯淀粉的制备与分析"", 《造纸化学品》 * |
| 百度文库: "MCR-3微波化学反应器使用说明书", 《 HTTP://WENKU.BAIDU.COM/LINK?URL=SZELAQKPX_DZUMT5IQHKKT7VEGXXRFIZ_YJLUV17N9SVNAEU6JHQMJUV4THUIWN1NXWPI8VNZ1RFJDCR2APN4YYQ6ZWX1JTZT7FKWVHJSFG》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418777A (en) * | 2015-12-19 | 2016-03-23 | 陈虹 | Synthetic process of acetylated starch |
| CN105542021A (en) * | 2016-02-01 | 2016-05-04 | 广西民族大学 | Method for producing starch acetate |
| CN112674209A (en) * | 2020-12-28 | 2021-04-20 | 华中农业大学 | Method for preparing acetylated starch capable of improving yield of fermented butyric acid |
| CN114805619A (en) * | 2022-06-15 | 2022-07-29 | 河南工业大学 | Preparation method of acetylated modified high-amylose corn starch |
| CN114805619B (en) * | 2022-06-15 | 2022-12-27 | 河南工业大学 | Preparation method of acetylated modified high-amylose corn starch |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102936290B (en) | 2015-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109627345B (en) | Preparation method and application of hydrophobic modified nanocellulose from sugarcane leaves | |
| CN101735392B (en) | Corn grafting starch and preparation method thereof | |
| CN102936290B (en) | Acetylated corn starch and preparation method thereof | |
| Mansouri et al. | Synthesis and characterization of carboxymethyl cellulose from tunisian vine stem: study of water absorption and retention capacities | |
| CN106832700B (en) | Polyvinyl alcohol and lac discard the composite foam material and preparation method thereof of refuse lac | |
| CN104910284A (en) | Double bond-containing modified starch as well as preparation method and application thereof | |
| CN102344495A (en) | Cyanoethyl cellulose glycerin ether and preparation method thereof | |
| CN103059148A (en) | Method for preparing acetate starch with mechanical activation solid phase reaction | |
| CN109487546A (en) | A kind of cation of high-efficiency environment friendly receives fibrillated fibers element preparation method | |
| Shuaiyang et al. | Preparation of xylan citrate—A potential adsorbent for industrial wastewater treatment | |
| CN105085689B (en) | The method of low temperature homogeneous catalytic transesterification preparing acetyl cellulose and cellulose mixed esters | |
| CN106917309A (en) | A kind of preparation method of corn stalk stalks of rice, wheat, etc. cellulose short-term training film | |
| CN102643390B (en) | Cationic grafted starch and preparation method thereof | |
| CN113914124A (en) | Modified nano-cellulose and application thereof in preparation of base paper | |
| CN106084259A (en) | A kind of preparation method of cellulose aquagel | |
| CN109024031A (en) | The method that steam blasting combination ultrasonic treatment prepares peanut shell nano-cellulose | |
| CN110511289A (en) | A kind of dual esterification starch slurry and preparation method thereof with low surface tension | |
| CN111303305A (en) | Method for preparing high-substitution-degree acetylated starch by electric field coupling ultrasound | |
| CN102690362A (en) | Preparation method for oxidation cross-linked-carboxymethyl composite modified starch, and oxidation cross-linked-carboxymethyl composite modified starch | |
| CN105693872A (en) | Preparation method of salt-resistant carboxymethyl starch | |
| CN105884912A (en) | Method for preparing cross-linked acetate starch by adopting wet process | |
| Mondal et al. | Utilization of cellulosic wastes in textile and garment industries: 2. Synthesis and characterization of cellulose acetate from knitted rag | |
| CN101597336A (en) | The microwave synthesis method of cellulose carbamate | |
| CN108409874A (en) | A kind of preparation method of high substituted degree etherificate cornstarch | |
| CN107540749A (en) | A kind of preparation method of acetic acid octanoic acid cellulose esters |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150527 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |